Lew azo dyestuffs



Patented Dec. 9, 1930 UNITED STATES PATENT orrics ERNST FELLMER, OF LEVERKUSEN-ON-THE-RHINE, GERMANY, ASSIGN OR TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., .A CORPORATION OF DELAWARE NEW AZO DYESTUFFS No Drawing. Application filed February25, 1928, Serial No; 257,098, and in Germany August 17, 1922.

This application is a continuation-in-part application of my application Ser. No. 64" 180, filed June 22, 1923, and relates to the preparation of new and valuable paradiamine azodyestuifs suitable for dyeing silk. These dyes can be obtained by combining the diazo compounds of paradiamines, e. paraphenylene diamines, which are substituted in one of the two amino groups by an acidyl radicle, e. g. forinyl, acetyl, oXal'yl etc. and in the benzene or naphthalene nucleus, by e. with azodyestuff components, splitting off the acidyl radicle by saponification, diazo tizing the resulting compound and combining it with a hydroxy naphthalenev sulfonic acid.

The new dyestuffs have most probably the general formula:

wherein X represents the residue of a pdiamine of the benzene or naphthalene series having not more than ten carbon atoms in nuclear linkage, Y represents a halogen, alkyl or alkoxy substituent, and R and R represent hydroxy-naphthalene sulfonic acid azo dyestuff coupling components the by droXy groups of which stand in o-position to the azo groups. The new a-zodyestufls are, after being dried and pulverized, in the shape of their alkali metal salts generally dark powders, soluble in concentrated sulfuric acid generally with a blue to bluish-green coloration, dyeing silk reddish-blue to black shades of excellent fastness to water which can be discharged to a pure white with hydrosulfite, which dyestufisupon reduction with stannous chloride and hydrochloric acid are split up into a substituted para diamine and two molecules of amino-naphthol-sulfonic acids.

In order to illustrate my new process more fully the following example is given, the parts being by weight:

EzmmpZa-MA parts of 5-amino-4-chloro- 2-oXalylaminol-anisol are dissolved in water together with sodium carbonate to a neutral solution which is acidulated at 5 C. and diazotized with 6.9 parts of sodium nitrite. The diazo-compound is then combined g. halogen, alkyl and alkoxygroups with 22A parts of 2-napthol-6-sulfonic acid. By boiling with 140 parts of a 30 per cent caustic soda lye, the oxalyl group is split off and.the aininoazocompound is isolated. by acidulation. It is stirred up'with water, dissolved in caustic soda lye, aoidulated, diazotized at 0 with 6, 9 parts of sodium nitrite and combined in 22,4 parts of l-hydroxynaphthalene-5-sulfon ic acid. The dye is isolated asusual.

It is after being dried and pulverized in the shape of its sodium salt a dark powder, soluble in cold water with a violet coloration,

. in hot water with a blue one and in concentrated sulfuric acid with a greenish blue coloration, yielding upon treatment with stannous chloride and hydrochloric acid 2.5- diamino e chloro l-anisol, 1-an1iuo-2hy droxynaphthalene-6-sulfonic acid and l-hydroXy-2-aminonaphthalene-5 sulfonic acid and dyeing silk pure blue shades fast to water which can be discharged to a pure white with hydrosulfite. The dye has in the free state most probably the formula:

soar BORE 7 Other diamines can be used c. g. l-acetyL amino4-annnonaphthalene-S-sulfonic acid, 5-am1no 4 chloro 2 .-,oxylylaminoanisol, 5- am1no-4-methyl-2-acetylamino'- l methoxybenzene, 5-am1no t-alkoXy-2-acetyl-amino-lalkoxy benzene, 2.5 dichloro 4 amino-'1- acetylaminobenzene, :&Il11I10l-&C6tflll11ll10- benzene-3-sulfonic acid etc. or other coupling components e. g. l-naphthoL l-sulfonic acid, 2- naphthol-3.6-d1sulfon1c acid, 2-naphthol-7- sulfonic acid, 2-am1no-8-naphthol-6-sulfonic acld, 2-am1no-8-naphthol-3-.S-disulfonic acid.

I claim: I

1. As new products the azodyestufi's havmg the general formula:

wherein X' represents the residue of a soda alkaline solution with a p-dithe group consisting o-position v chloride and liydi'ocliloricacid, are split up into a substituted paraHdiamino-compound the 5 1 5 lrts Sodium amineof the benzene or naphthalene series having not more than ten carbon atoms in nuclear linkage, Y represents a substituent of and R and R represent a hyd'roxynaphthalene sulfonic acid azodyestuii coupling component, the hydroxy groups ofwhich stand in to the azo groups, which a'zodyestuffs are,

' 10 the shape of their alkali metal 'Sfiltfidfllk} powders soluble in concentrated sulfurio'aci generally with a tion, dyeing silk reddish-blueto discharged'to'a pure white with hydrosulfite,

whichdyestufis upon reduction with stan nous andtwo molecules [of amino-nap]ithol-sul'f fonic acid.

I 2. As newproducts the azodystuilshaving the. generalzformula V 3 V whereint Y represents a A substituent For, the halogemalkyl group comprising hydrogen, and alkoxy, and R and R represent hydroxynaphthalene sulfonic acid azodye'stuif couplingcomponents, the hydroxygroups of which stand in ortho-position to the azo alk'ali metal salts dark concentrated sulfuricv acid groups which azodyestuffs are, after being dried and pulverized in the shape of their powders soluble v in generally with a blue to bluish green coloration, dyeing silk reddish-blue to blackshadesof excellent fastness to water which can pure white with hydrosulfite, which dyestuffs hydrochloric acid, are tuted para-diamino compound and'two mole- 'cules of amino-naphthol-sulfonic acid; 7

- 4, Asia new product the azodyestufi havof halogen, alkyl, alkoxy after being dried andpulveri'zed', inf

blue to bluish green colon-y 7, black: shades v of excellent {fitness t0 water which can be.

; (.lyestuifs'blaimed in claim 2.

be discharged to a I ness to'water which can be discharged to a 'pure white with hydrosulfite, which dyestuffs upon reduction with stannous chloride and split up into a substiing 'in the freefstate most probably the formulaz" i "on; on"

i V ,1; is SOzH I which after being dried and mltrized in salt a "dark "powdersolublein coldcwa'ter with a violet c'olora' tion, in water with a blue one and in c011 1 cent-rated sulfuric ac d w th a greenish-blue coloration, yieldingYupontreatment with stannous chloride 'and hydrochloric acid 2.5-d am1no 4-chloro-1;anisol, l amino-fl-hydroxynaphthal'ene-6-sulfonic acid and l-hy dr'oxy-2 aminonaphthalene-fi-sulionic acid; I s and dyeing silk pureblue shades fast to water which can be dischargedto a pure white with hydrosulfite.

5-p'As ainew product-psilk dyed with the dyestuffs claimed in claim 1. p I I 6.;As a, new product, silk dyed with the '7. As a new product, silk dyestuffs claimed in claim 3. r a

8. As .a new product, silk dyed with the dyestu'if claimed in claim 4. I In testimony whereof I have hereunto set myhand' ERNST FELLMER.

upon IGdUCtlOILWlth stannous chloride and hydrochloric? acid, split up into a substituted 7 para dia'mino-compound and two molecules of amino-naphthol-sulfonic acid. '1 I 3. As new products the azodyestuffs having the general formula: V

dyed with the whereinY'represents a substituent o ff the" group comprising hydrogen, halogen, alkyl R and R represent a T and alkoxy, and hydroxy-naphtlialene sulfonic acid azodyestuff couplingcomponent, the hydroxy groups stand in ortho-position'to the azo;

groups, which'azodyestulis are, after being dried and pulverized, in the shape of their alkali metal salts, dark powders soluble in concentrated sulfuric acid generally with a blueto bluish green coloration, dyeing silk reddish-blue to black shades of excellent fast- 

